WO2023082507A1 - Composite material based on caffeic acid and preparation method therefor - Google Patents

Composite material based on caffeic acid and preparation method therefor Download PDF

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WO2023082507A1
WO2023082507A1 PCT/CN2022/080304 CN2022080304W WO2023082507A1 WO 2023082507 A1 WO2023082507 A1 WO 2023082507A1 CN 2022080304 W CN2022080304 W CN 2022080304W WO 2023082507 A1 WO2023082507 A1 WO 2023082507A1
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cyclodextrin
caffeic acid
organic framework
metal
preparation
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PCT/CN2022/080304
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French (fr)
Chinese (zh)
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丁甜
沈默斐
冯劲松
刘东红
陈士国
徐恩波
王文骏
程焕
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浙江大学
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Priority to US18/277,559 priority Critical patent/US20240122178A1/en
Publication of WO2023082507A1 publication Critical patent/WO2023082507A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof

Definitions

  • the present application relates to the technical field of antibacterial materials, in particular to a composite material based on caffeic acid and a preparation method thereof.
  • Metal-Organic Frameworks are porous coordination materials composed of multi-dentate organic ligands and metal ions or metal clusters, which are connected by coordination bonds or covalent bonds between metal ion centers and organic ligands. Formed infinite network structure. It has the advantages of large specific surface area, adjustable function, high porosity, etc. It is a rapidly developing new porous material with broad application prospects.
  • Cyclodextrins are naturally occurring cyclic oligosaccharides that are produced by cyclodextrin glycosyltransferases during the enzymatic degradation of starch. Cyclodextrins usually contain 6-12 D-glucopyranose units, among which molecules with 6, 7, and 8 glucose units are of great practical significance, called ⁇ -, ⁇ -, and ⁇ -cyclodextrins, respectively. Cyclodextrin metal-organic frameworks make cyclodextrin and alkali metal ions form a new metal-organic framework through organic coordination.
  • this material Compared with traditional metal-organic frameworks, this material has good water solubility and non-toxicity, and It has the characteristics of porous and large specific surface area, and its huge cavity can play a protective role. It has become a research hotspot as a delivery material.
  • Caffeic acid is an organic acid that exists in a variety of foods. In addition to food, caffeic acid also exists in common health medicines such as propolis. It has good antioxidant, antibacterial and other biological effects. However, caffeic acid and The poor chemical and physical stability of its derivatives limits its application. There is an urgent need in the art to develop materials and methods to improve the stability of caffeic acid.
  • the purpose of this application is to provide a composite material based on caffeic acid and its preparation method, which can solve the problem in the prior art that it is urgent to develop materials and methods for improving the stability of caffeic acid.
  • a preparation method of a composite material based on caffeic acid comprising:
  • the ratio of the cyclodextrin metal organic framework material to the short-chain alcohol solution of caffeic acid is that the molar ratio of ⁇ -cyclodextrin to caffeic acid in the cyclodextrin metal organic framework material is 1:25-70 count.
  • the incubation time is 500 min to 1000 min.
  • the temperature of the incubation treatment is 30°C-60°C.
  • the ratio of the cyclodextrin metal organic framework material to the short-chain alcohol solution of caffeic acid is such that the molar ratio of ⁇ -cyclodextrin to caffeic acid in the cyclodextrin metal organic framework material is 1:60-70
  • the time of the incubation treatment is 850-950 min; the temperature of the incubation treatment is 35-45°C.
  • the ratio of the cyclodextrin metal organic framework material to the short-chain alcohol solution of caffeic acid is that the molar ratio of ⁇ -cyclodextrin to caffeic acid in the cyclodextrin metal organic framework material is 1:64;
  • the time of the incubation treatment is 900min; the temperature of the incubation treatment is 40°C.
  • the cyclodextrin metal organic framework material is prepared by the following method:
  • the aqueous solution dispersed with ⁇ -cyclodextrin and potassium hydroxide is ultrasonically mixed and then placed in a water bath for water bath reaction. After the water bath reaction is completed, ultrasonically again and polyethylene glycol is added to the resulting mixed solution while ultrasonically to obtain a crude product ; The obtained crude product is washed and dried to obtain the cyclodextrin metal organic framework material;
  • the molar ratio of ⁇ -cyclodextrin to potassium hydroxide in the aqueous solution is 1:5-10.
  • the potassium ions in the cyclodextrin metal organic framework material CD-MOF are in the form of 8 coordination, which can make 6 ⁇ -cyclodextrins constitute the smallest building unit of CD-MOF, which is equivalent to 2 potassium ions and 1
  • a pair of ⁇ -cyclodextrins has a chemical formula of [(C 48 H 80 O 40 )(KOH) 2 ] n , and excess potassium hydroxide is beneficial for all ⁇ -cyclodextrins to participate in the reaction.
  • the polyethylene glycol has a molecular weight of 8000, and the molar ratio of the added polyethylene glycol to ⁇ -cyclodextrin is 0.06-0.07:1;
  • the temperature of the water bath reaction is 55°C-65°C.
  • the short-chain alcohol is absolute methanol or absolute ethanol. It is advisable to use short-chain alcohols as solvents to fully dissolve the reactants.
  • the dynamic contact means that the cyclodextrin metal organic framework material and the caffeic acid are in a dynamic process during the reaction, not in a static state, such as by stirring, or by shaking.
  • the dynamic contact is stirring or shaking; the rotation speed of stirring or shaking is 100rpm-400rpm.
  • post-treatment is also included after the incubation treatment is completed, and the post-treatment includes: centrifuging the mixed solution after the incubation treatment, discarding the supernatant and then vacuum-drying.
  • the vacuum drying condition is: vacuum drying at 40-60° C. for 4-6 hours.
  • the present application also provides a caffeic acid-based composite material prepared by the preparation method described in the above technical solution.
  • the caffeic acid-based composite material includes a cyclodextrin metal organic framework material prepared from ⁇ -cyclodextrin and caffeic acid loaded on the cyclodextrin metal organic framework material, and the caffeic acid
  • the loading amount of the caffeic acid is 15-18% of the total mass of the composite material based on caffeic acid; the caffeic acid is in the cavity of the cyclodextrin metal organic framework.
  • the present application provides a composite material based on caffeic acid derivatives, the composite material based on caffeic acid derivatives includes a cyclodextrin metal organic framework material prepared from ⁇ -cyclodextrin and a metal loaded on the cyclodextrin A caffeic acid derivative on an organic framework material; the caffeic acid derivative is in the cavity of a cyclodextrin metal organic framework.
  • the method for loading caffeic acid by using cyclodextrin metal organic framework material in the present application is simple in operation, mild in reaction, and achieves a higher loading rate of caffeic acid.
  • the caffeic acid-loaded cyclodextrin metal organic framework material prepared by the method of the present application has relatively uniform particle size, obvious XRD diffraction peaks, good crystal characteristics, and good thermal and chemical stability, and can be applied to food, environment, etc. applied research in the field.
  • Figure 1 is a graph showing the effect of the molar ratio of gamma-cyclodextrin and caffeic acid on the loading rate of caffeic acid in the cyclodextrin metal-organic framework compound;
  • Figure 2 is a graph showing the effect of the incubation time of cyclodextrin metal-organic frameworks and caffeic acid on the loading rate of caffeic acid;
  • Figure 3 is a graph showing the effect of the incubation temperature of cyclodextrin metal-organic framework complexes and caffeic acid on the loading rate of caffeic acid;
  • Fig. 4 is the powder X-ray diffraction spectrum of the cyclodextrin metal-organic framework composite of loading caffeic acid in embodiment 1;
  • Figure 5 is a scanning electron microscope image of a cyclodextrin metal organic framework compound loaded with caffeic acid in Example 1;
  • Fig. 6 is the infrared spectrogram of the cyclodextrin metal-organic framework compound loaded with caffeic acid in Example 1;
  • Fig. 7 is the thermal gravimetric spectrum of the cyclodextrin metal-organic framework compound loaded with caffeic acid in Example 1;
  • Fig. 8 is a comparison result graph of the caffeic acid loading rate between cyclodextrin metal organic framework and equimolar amount of ⁇ -cyclodextrin.
  • cyclodextrin metal organic framework materials to load caffeic acid can solve the problem of poor chemical and physical stability of caffeic acid and its derivatives: adding cyclodextrin metal organic framework materials to short chains containing caffeic acid In the alcohol solution, stirring and incubating at a certain speed is carried out, so as to obtain the cyclodextrin metal-organic framework complex loaded with caffeic acid.
  • the ratio of different cyclodextrin metal organic framework materials to caffeic acid ( ⁇ -cyclodextrin and caffeic acid in cyclodextrin metal organic framework materials
  • the molar ratios are 1:4, 1:8, 1:32, 1:64 and 1:128) respectively, the effect on the loading rate of caffeic acid, the results are shown in Figure 1, in the cyclodextrin metal organic framework compound
  • the loading rate of caffeic acid exceeds 10%.
  • the loading rate of caffeic acid gradually increases, and the loading rate increases after increasing to 1:64. It is no longer obvious, therefore, the molar ratio of ⁇ -cyclodextrin to caffeic acid in the cyclodextrin metal organic framework material is selected from 1:4 to 1:128, further selected from 1:32 to 1:128; further selected from Choose from 1:25 to 1:70; further choose from 1:60 to 70; most preferably 1:64.
  • CD-MOF cyclodextrin metal organic framework
  • ⁇ -cyclodextrin and metal ions form a cyclodextrin metal-organic framework with a body-centered cubic structure, and the cyclodextrin metal-organic framework forms a complex with caffeic acid, in which the cyclodextrin metal-organic framework does not destroy ⁇ -cyclodextrin
  • the ⁇ -cyclodextrin used is all composed of cyclodextrin metal organic frameworks. Therefore, in the actual experiment process, cyclodextrin metal organic framework materials can also be prepared The molar ratio of ⁇ -cyclodextrin to caffeic acid was converted.
  • the reaction temperature is preferably 30 °C ⁇ 60 °C ; More preferably 35°C to 45°C; most preferably 40°C.
  • the content (w/w) of caffeic acid in the compound prepared by the present application is ⁇ 5%, preferably ⁇ 10%, more preferably ⁇ 15%.
  • thermogravimetric loss of caffeic acid in the caffeic acid-based composite material is higher than that of free caffeic acid 13% reduction, as shown in Figure 7.
  • the present application also found through experiments that under optimal loading conditions ( ⁇ -cyclodextrin:caffeic acid molar ratio in cyclodextrin metal organic framework complex is 1:64, loading time is 900 minutes, loading temperature is 40°C) , the drug loading rate of cyclodextrin metal organic framework to caffeic acid can reach 16.52%, which is higher than the drug loading rate of caffeic acid with the same molar amount of ⁇ -cyclodextrin, which is 7.28%.
  • the powder X-ray diffraction pattern of the caffeic acid-loaded cyclodextrin metal-organic framework composite synthesized in this example is shown in Figure 4. From Figure 4, it can be seen that the caffeic acid-loaded cyclodextrin metal-organic framework composite prepared in this example The position of the peak in the XRD pattern of the shelf coincides with that of the metal-organic framework of cyclodextrin, indicating that the loading of caffeic acid will not destroy the structure of the metal-organic framework of cyclodextrin; The characteristic peak of caffeic acid in the XRD pattern of the mixture disappeared, indicating that caffeic acid was in the cavity of cyclodextrin metal-organic framework.
  • the infrared spectrum of the caffeic acid-loaded cyclodextrin metal-organic framework compound synthesized in this example is shown in Figure 6, and the infrared spectrum of the caffeic acid-loaded cyclodextrin metal-organic framework compound prepared in this example shows a peak The position coincides with the metal-organic framework of cyclodextrin, indicating that the loading of caffeic acid will not destroy the structure of the metal-organic framework of cyclodextrin; compared with the infrared spectrum of caffeic acid and the physical blend of caffeic acid and cyclodextrin metal-organic framework The characteristic peaks of caffeic acid became weaker or even partially disappeared, indicating that caffeic acid was in the cavity of cyclodextrin metal-organic framework. In this example, the product of the target structure was obtained.

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Abstract

Disclosed in the present application are a composite material based on caffeic acid and a preparation method therefor. The method comprises: exposing a cyclodextrin metal-organic framework material prepared from γ-cyclodextrin to a short-chain alcohol solution of caffeic acid, and performing incubation, wherein during the incubation, the cyclodextrin metal-organic framework material is in dynamic contact with the short-chain alcohol solution of caffeic acid. The prepared composite material comprises a cyclodextrin metal-organic framework material prepared from γ-cyclodextrin and caffeic acid loaded on the cyclodextrin metal-organic framework material, wherein the loading amount of caffeic acid is 15%-18% of the total mass of the complex, and the caffeic acid is located in a cavity of the cyclodextrin metal-organic framework. The complex of the present application has a relatively uniform particle size, obvious XRD diffraction peaks, good crystal characteristics, and good thermal stability and chemical stability, and can be applied to application research in the fields of food, environment, etc.

Description

一种基于咖啡酸的复合材料及其制备方法A kind of composite material based on caffeic acid and preparation method thereof
本申请要求于2021年11月10日提交中国专利局、申请号为CN202111328172.8、发明名称为“一种基于咖啡酸的复合材料及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application submitted to the China Patent Office on November 10, 2021 with the application number CN202111328172.8 and the title of the invention "a composite material based on caffeic acid and its preparation method", the entire content of which Incorporated in this application by reference.
技术领域technical field
本申请涉及抗菌材料技术领域，具体涉及一种基于咖啡酸的复合材料及其制备方法。The present application relates to the technical field of antibacterial materials, in particular to a composite material based on caffeic acid and a preparation method thereof.
背景技术Background technique
金属有机框架材料(Metal-Organic Frameworks，MOFs)是由多齿有机配体和金属离子或金属簇组成的多孔配位材料，是通过金属离子中心与有机配体的配位键或共价键连接形成的无限网络结构。它具有比表面积大、可调功能、高孔隙率等优点，是一种快速发展的新型多孔材料，具有广阔的应用前景。Metal-Organic Frameworks (MOFs) are porous coordination materials composed of multi-dentate organic ligands and metal ions or metal clusters, which are connected by coordination bonds or covalent bonds between metal ion centers and organic ligands. Formed infinite network structure. It has the advantages of large specific surface area, adjustable function, high porosity, etc. It is a rapidly developing new porous material with broad application prospects.
环糊精是天然存在的环状寡糖，是在淀粉的酶促降解过程中由环糊精糖基转移酶产生的。环糊精通常含有6-12个D-吡喃葡萄糖单元，其中具有重要实际意义的是含有6、7、8个葡萄糖单元的分子，分别称α-，β-，γ-环糊精。环糊精金属有机框架通过有机配位的方式使环糊精以及碱金属离子形成一种新的金属有机框架，这种材料相对于传统的金属有机框架，具有良好的水溶性和无毒性，并具有多孔、比表面积大等特点，其巨大空腔能起到保护作用，目前已作为递送材料成为研究的热点。Cyclodextrins are naturally occurring cyclic oligosaccharides that are produced by cyclodextrin glycosyltransferases during the enzymatic degradation of starch. Cyclodextrins usually contain 6-12 D-glucopyranose units, among which molecules with 6, 7, and 8 glucose units are of great practical significance, called α-, β-, and γ-cyclodextrins, respectively. Cyclodextrin metal-organic frameworks make cyclodextrin and alkali metal ions form a new metal-organic framework through organic coordination. Compared with traditional metal-organic frameworks, this material has good water solubility and non-toxicity, and It has the characteristics of porous and large specific surface area, and its huge cavity can play a protective role. It has become a research hotspot as a delivery material.
咖啡酸是一种存在于多种食物中的有机酸，除食品外，咖啡酸还存在于蜂胶等常见的保健药物中，具有良好的抗氧化、抗菌等多种生物学功效，然而咖啡酸及其衍生物的化学和物理稳定性较差并限制了其应用。本领域迫切需要开发提高咖啡酸稳定性的材料和方法。Caffeic acid is an organic acid that exists in a variety of foods. In addition to food, caffeic acid also exists in common health medicines such as propolis. It has good antioxidant, antibacterial and other biological effects. However, caffeic acid and The poor chemical and physical stability of its derivatives limits its application. There is an urgent need in the art to develop materials and methods to improve the stability of caffeic acid.
发明内容Contents of the invention
本申请的目的在于提供一种基于咖啡酸的复合材料及其制备方法，可解决现有技术中迫切需要开发提高咖啡酸稳定性的材料和方法的难题。The purpose of this application is to provide a composite material based on caffeic acid and its preparation method, which can solve the problem in the prior art that it is urgent to develop materials and methods for improving the stability of caffeic acid.
一种基于咖啡酸的复合材料的制备方法，包括：A preparation method of a composite material based on caffeic acid, comprising:
将由γ-环糊精制备得到的环糊精金属有机框架材料暴露于咖啡酸的短链醇溶液中，孵育处理；孵育处理过程中所述环糊精金属有机框架材料与咖啡酸的短链醇溶液动态接触。Expose the cyclodextrin metal-organic framework material prepared by gamma-cyclodextrin to a short-chain alcohol solution of caffeic acid, and incubate; during the incubation process, the cyclodextrin metal-organic framework material and the short-chain alcohol of caffeic acid solutions in dynamic contact.
可选的，所述环糊精金属有机框架材料与咖啡酸的短链醇溶液的配比以环糊精金属有机框架材料中γ-环糊精与咖啡酸的摩尔比为1：25～70计。Optionally, the ratio of the cyclodextrin metal organic framework material to the short-chain alcohol solution of caffeic acid is that the molar ratio of γ-cyclodextrin to caffeic acid in the cyclodextrin metal organic framework material is 1:25-70 count.
可选的，所述孵育处理的时间为500min～1000min。Optionally, the incubation time is 500 min to 1000 min.
可选的，所述孵育处理的温度为30℃～60℃。Optionally, the temperature of the incubation treatment is 30°C-60°C.
进一步优选地，所述环糊精金属有机框架材料与咖啡酸的短链醇溶液的配比以环糊精金属有机框架材料中γ-环糊精与咖啡酸的摩尔比为1：60～70计；所述孵育处理的时间为850～950min；所述孵育处理的温度为35～45℃。Further preferably, the ratio of the cyclodextrin metal organic framework material to the short-chain alcohol solution of caffeic acid is such that the molar ratio of γ-cyclodextrin to caffeic acid in the cyclodextrin metal organic framework material is 1:60-70 The time of the incubation treatment is 850-950 min; the temperature of the incubation treatment is 35-45°C.
最优选的，所述环糊精金属有机框架材料与咖啡酸的短链醇溶液的配比以环糊精金属有机框架材料中γ-环糊精与咖啡酸的摩尔比为1：64；所述孵育处理的时间为900min；所述孵育处理的温度为40℃。Most preferably, the ratio of the cyclodextrin metal organic framework material to the short-chain alcohol solution of caffeic acid is that the molar ratio of γ-cyclodextrin to caffeic acid in the cyclodextrin metal organic framework material is 1:64; The time of the incubation treatment is 900min; the temperature of the incubation treatment is 40°C.
可选的，所述环糊精金属有机框架材料由如下方法制备：Optionally, the cyclodextrin metal organic framework material is prepared by the following method:
将同时分散有γ-环糊精和氢氧化钾的水溶液超声混合后置于水浴中进行水浴反应，水浴反应结束后再次超声并在超声同时向所得混合液中加入聚乙二醇，得粗产物；将所得粗产物经洗涤、干燥后即得所述环糊精金属有机框架材料；The aqueous solution dispersed with γ-cyclodextrin and potassium hydroxide is ultrasonically mixed and then placed in a water bath for water bath reaction. After the water bath reaction is completed, ultrasonically again and polyethylene glycol is added to the resulting mixed solution while ultrasonically to obtain a crude product ; The obtained crude product is washed and dried to obtain the cyclodextrin metal organic framework material;
可选的，所述水溶液中γ-环糊精和氢氧化钾的摩尔比为1：5～10。通常情况下，环糊精金属有机框架材料CD-MOF中的钾离子为8配位形式，可以使6个γ-环糊精组成CD-MOF的最小构筑单元，相当于2个钾离子与1个γ-环糊精配对，化学式为[(C 48H 80O 40)(KOH) 2] n，而过量氢氧化钾有利于γ-环糊精全部参与反应。 Optionally, the molar ratio of γ-cyclodextrin to potassium hydroxide in the aqueous solution is 1:5-10. Usually, the potassium ions in the cyclodextrin metal organic framework material CD-MOF are in the form of 8 coordination, which can make 6 γ-cyclodextrins constitute the smallest building unit of CD-MOF, which is equivalent to 2 potassium ions and 1 A pair of γ-cyclodextrins has a chemical formula of [(C 48 H 80 O 40 )(KOH) 2 ] n , and excess potassium hydroxide is beneficial for all γ-cyclodextrins to participate in the reaction.
可选的，所述聚乙二醇的分子量8000，加入的聚乙二醇与γ-环糊精的摩尔比为0.06～0.07：1；Optionally, the polyethylene glycol has a molecular weight of 8000, and the molar ratio of the added polyethylene glycol to γ-cyclodextrin is 0.06-0.07:1;
可选的，所述水浴反应的温度为55℃～65℃。Optionally, the temperature of the water bath reaction is 55°C-65°C.
可选的，所述短链醇为无水甲醇或无水乙醇。短链醇作为溶剂，以充分溶解反应物为宜。Optionally, the short-chain alcohol is absolute methanol or absolute ethanol. It is advisable to use short-chain alcohols as solvents to fully dissolve the reactants.
所述动态接触是指在反应过程中环糊精金属有机框架材料和咖啡酸 之间处于动态过程，非静止状态，例如通过搅拌实现，也可以通过振荡实现。The dynamic contact means that the cyclodextrin metal organic framework material and the caffeic acid are in a dynamic process during the reaction, not in a static state, such as by stirring, or by shaking.
可选的，所述动态接触为搅拌或震荡；搅拌或震荡的转速为100rpm～400rpm。Optionally, the dynamic contact is stirring or shaking; the rotation speed of stirring or shaking is 100rpm-400rpm.
可选的，孵育处理完成后还包括后处理，所述后处理包括：将孵育处理完成后的混合液离心，弃去上清液后进行真空干燥。Optionally, post-treatment is also included after the incubation treatment is completed, and the post-treatment includes: centrifuging the mixed solution after the incubation treatment, discarding the supernatant and then vacuum-drying.
可选的，所述真空干燥的条件为：40～60℃条件下真空干燥4～6小时。Optionally, the vacuum drying condition is: vacuum drying at 40-60° C. for 4-6 hours.
本申请还提供上述技术方案所述制备方法制备得到的基于咖啡酸的复合材料。在本发明中，所述基于咖啡酸的复合材料包括由γ-环糊精制备的环糊精金属有机框架材料和负载于所述环糊精金属有机框架材料上的咖啡酸，所述咖啡酸的负载量为基于咖啡酸的复合材料总质量的15～18％；所述咖啡酸处于环糊精金属有机框架的空腔内。The present application also provides a caffeic acid-based composite material prepared by the preparation method described in the above technical solution. In the present invention, the caffeic acid-based composite material includes a cyclodextrin metal organic framework material prepared from γ-cyclodextrin and caffeic acid loaded on the cyclodextrin metal organic framework material, and the caffeic acid The loading amount of the caffeic acid is 15-18% of the total mass of the composite material based on caffeic acid; the caffeic acid is in the cavity of the cyclodextrin metal organic framework.
本申请提供了一种基于咖啡酸衍生物的复合材料，所述基于咖啡酸衍生物的复合材料包括由γ-环糊精制备的环糊精金属有机框架材料和负载于所述环糊精金属有机框架材料上的咖啡酸衍生物；所述咖啡酸衍生物处于环糊精金属有机框架的空腔内。The present application provides a composite material based on caffeic acid derivatives, the composite material based on caffeic acid derivatives includes a cyclodextrin metal organic framework material prepared from γ-cyclodextrin and a metal loaded on the cyclodextrin A caffeic acid derivative on an organic framework material; the caffeic acid derivative is in the cavity of a cyclodextrin metal organic framework.
与现有技术相比，本申请具有如下有益效果：Compared with the prior art, the present application has the following beneficial effects:
本申请利用环糊精金属有机框架材料负载咖啡酸的方法操作简单，反应温和，实现对咖啡酸较高的负载率。本申请方法制备得到的负载咖啡酸的环糊精金属有机框架材料，粒径相对均一，XRD衍射峰明显，具有良好晶体特征，并且热稳定性和化学稳定性良好，可应用于食品、环境等领域的应用研究。The method for loading caffeic acid by using cyclodextrin metal organic framework material in the present application is simple in operation, mild in reaction, and achieves a higher loading rate of caffeic acid. The caffeic acid-loaded cyclodextrin metal organic framework material prepared by the method of the present application has relatively uniform particle size, obvious XRD diffraction peaks, good crystal characteristics, and good thermal and chemical stability, and can be applied to food, environment, etc. applied research in the field.
说明书附图Instructions attached
图1为环糊精金属有机框架复合物中γ-环糊精与咖啡酸的摩尔比例对咖啡酸负载率的影响结果图；Figure 1 is a graph showing the effect of the molar ratio of gamma-cyclodextrin and caffeic acid on the loading rate of caffeic acid in the cyclodextrin metal-organic framework compound;
图2为环糊精金属有机框架与咖啡酸的孵育时间对咖啡酸负载率的影响结果图；Figure 2 is a graph showing the effect of the incubation time of cyclodextrin metal-organic frameworks and caffeic acid on the loading rate of caffeic acid;
图3为环糊精金属有机框架复合物与咖啡酸的孵育温度对咖啡酸负载率的影响结果图；Figure 3 is a graph showing the effect of the incubation temperature of cyclodextrin metal-organic framework complexes and caffeic acid on the loading rate of caffeic acid;
图4为实施例1中负载咖啡酸的环糊精金属有机框架复合物的粉末X 射线衍射图谱；Fig. 4 is the powder X-ray diffraction spectrum of the cyclodextrin metal-organic framework composite of loading caffeic acid in embodiment 1;
图5为实施例1中负载咖啡酸的环糊精金属有机框架复合物的扫描电子显微镜图；Figure 5 is a scanning electron microscope image of a cyclodextrin metal organic framework compound loaded with caffeic acid in Example 1;
图6为实施例1中负载咖啡酸的环糊精金属有机框架复合物的红外光谱图；Fig. 6 is the infrared spectrogram of the cyclodextrin metal-organic framework compound loaded with caffeic acid in Example 1;
图7为实施例1中负载咖啡酸的环糊精金属有机框架复合物的热重谱图；Fig. 7 is the thermal gravimetric spectrum of the cyclodextrin metal-organic framework compound loaded with caffeic acid in Example 1;
图8为环糊精金属有机框架与等摩尔量的γ-环糊精对咖啡酸负载率的对比结果图。Fig. 8 is a comparison result graph of the caffeic acid loading rate between cyclodextrin metal organic framework and equimolar amount of γ-cyclodextrin.
具体实施方式Detailed ways
下面将结合实施例对本申请的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。The technical solutions of the present application will be clearly and completely described below in conjunction with the embodiments. Apparently, the described embodiments are only some of the embodiments of the present application, not all of them. Based on the embodiments in this application, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the scope of protection of this application.
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请。Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which this application belongs. The terms used herein in the specification of the application are only for the purpose of describing specific embodiments, and are not intended to limit the application.
本申请发现采用环糊精金属有机框架材料负载咖啡酸，可解决咖啡酸及其衍生物的化学和物理稳定性较差的问题：将环糊精金属有机框架材料添加至含咖啡酸的短链醇溶液中，进行一定转速搅拌孵育处理，从而获得负载咖啡酸的环糊精金属有机框架复合物。The present application found that the use of cyclodextrin metal organic framework materials to load caffeic acid can solve the problem of poor chemical and physical stability of caffeic acid and its derivatives: adding cyclodextrin metal organic framework materials to short chains containing caffeic acid In the alcohol solution, stirring and incubating at a certain speed is carried out, so as to obtain the cyclodextrin metal-organic framework complex loaded with caffeic acid.
一种实施方式中，以反应温度为40℃、反应时间为900min，对比了不同环糊精金属有机框架材料与咖啡酸配比(环糊精金属有机框架材料中γ-环糊精与咖啡酸摩尔比例分别为1：4、1：8、1：32、1：64和1：128)下对咖啡酸的负载率影响，结果如如图1所示，环糊精金属有机框架复合物中γ-环糊精与咖啡酸的摩尔比为1：4时，咖啡酸的负载率超过10％，随着咖啡酸用量的增加，咖啡酸负载量逐步上升，增加至1：64后负载率增加不再明显，因此，环糊精金属有机框架材料中γ-环糊精与咖啡酸摩尔比从1：4～1：128中选择，进一步的从1：32～1：128中选择；进一步从1：25～1：70中选择；更进一步从1：60～70中选择；最优选为1：64。In one embodiment, with a reaction temperature of 40°C and a reaction time of 900 min, the ratio of different cyclodextrin metal organic framework materials to caffeic acid (γ-cyclodextrin and caffeic acid in cyclodextrin metal organic framework materials The molar ratios are 1:4, 1:8, 1:32, 1:64 and 1:128) respectively, the effect on the loading rate of caffeic acid, the results are shown in Figure 1, in the cyclodextrin metal organic framework compound When the molar ratio of γ-cyclodextrin to caffeic acid is 1:4, the loading rate of caffeic acid exceeds 10%. With the increase of the amount of caffeic acid, the loading rate of caffeic acid gradually increases, and the loading rate increases after increasing to 1:64. It is no longer obvious, therefore, the molar ratio of γ-cyclodextrin to caffeic acid in the cyclodextrin metal organic framework material is selected from 1:4 to 1:128, further selected from 1:32 to 1:128; further selected from Choose from 1:25 to 1:70; further choose from 1:60 to 70; most preferably 1:64.
环糊精金属有机框架材料(CD-MOF)的最小构筑单元的化学式为[(C 48H 80O 40)(KOH) 2] 6，因此可近似将CD-MOF的相对分子量看作8112，其中1分子量CD-MOF含有6个γ-环糊精，即1mol的CD-MOF中含有6mol的γ-环糊精。 The chemical formula of the smallest building block of cyclodextrin metal organic framework (CD-MOF) is [(C 48 H 80 O 40 )(KOH) 2 ] 6 , so the relative molecular weight of CD-MOF can be approximately regarded as 8112, where 1 molecular weight CD-MOF contains 6 γ-cyclodextrin, that is, 1 mol of CD-MOF contains 6 mol of γ-cyclodextrin.
γ-环糊精与金属离子形成具有体心立方结构的环糊精金属有机框架，环糊精金属有机框架与咖啡酸形成复合物，其中环糊精金属有机框架不会破坏γ-环糊精的结构，也可以理解为在金属离子过量的情况下，所用的γ-环糊精全部组成为环糊精金属有机框架，因此，在实际实验过程中，也可以制备环糊精金属有机框架材料的γ-环糊精与咖啡酸的摩尔比进行换算。γ-cyclodextrin and metal ions form a cyclodextrin metal-organic framework with a body-centered cubic structure, and the cyclodextrin metal-organic framework forms a complex with caffeic acid, in which the cyclodextrin metal-organic framework does not destroy γ-cyclodextrin It can also be understood that in the case of excessive metal ions, the γ-cyclodextrin used is all composed of cyclodextrin metal organic frameworks. Therefore, in the actual experiment process, cyclodextrin metal organic framework materials can also be prepared The molar ratio of γ-cyclodextrin to caffeic acid was converted.
一种实施方式中，在环糊精金属有机框架材料中γ-环糊精与咖啡酸摩尔比1：64、反应温度为40℃条件下对比了不同孵育时间(10，20，60，180，360，720，900，2160分钟)下对咖啡酸负载率影响，结果如图2所示，随着时间的延长，咖啡酸的负载量逐步上升，至一定程度后再不增加，因此，环糊精金属有机框架与咖啡酸孵育时间在500min～1000min中选择。In one embodiment, different incubation times (10, 20, 60, 180, 360, 720, 900, 2160 minutes) on the loading rate of caffeic acid, the results are shown in Figure 2, with the prolongation of time, the loading of caffeic acid gradually increases, and does not increase after reaching a certain level. Therefore, cyclodextrin The incubation time between metal organic framework and caffeic acid is selected from 500min to 1000min.
一种实施方式中，在环糊精金属有机框架材料中γ-环糊精与咖啡酸摩尔比1：64、反应时间为900min条件下对比了不同温度(20℃、30℃、40℃、50℃和60℃)下对咖啡酸负载率影响，结果如图3所示，在30℃～60℃范围内γ-酸的负载量均能达到15％，因此，反应温度优选30℃～60℃；进一步优选35℃～45℃；最优选为40℃。In one embodiment, different temperatures (20°C, 30°C, 40°C, 50°C, 20°C, 30°C, 40°C, ℃ and 60 ℃) on the loading rate of caffeic acid, the results are shown in Figure 3, in the range of 30 ℃ ~ 60 ℃ γ-acid loading can reach 15%, therefore, the reaction temperature is preferably 30 ℃ ~ 60 ℃ ; More preferably 35°C to 45°C; most preferably 40°C.
本申请制备得到的复合物中咖啡酸的含量(w/w)≥5％，较佳地≥10％，更佳地≥15％。The content (w/w) of caffeic acid in the compound prepared by the present application is ≥5%, preferably ≥10%, more preferably ≥15%.
本申请的基于咖啡酸的复合材料热稳定性和化学稳定性得到显著改善，在咖啡酸分解温度230℃时，基于咖啡酸的复合材料中咖啡酸的热重损失比游离咖啡酸的热重损失减少13％，如图7所示。The thermal stability and chemical stability of the caffeic acid-based composite material of the present application are significantly improved. When the caffeic acid decomposition temperature is 230 ° C, the thermogravimetric loss of caffeic acid in the caffeic acid-based composite material is higher than that of free caffeic acid 13% reduction, as shown in Figure 7.
在最优反应条件(环糊精金属有机框架复合物中γ-环糊精：咖啡酸比例为1：64、负载时间为900分钟、负载温度为40℃)下，制备得到的复合物中咖啡酸的负载率比采用同等摩尔量的γ-环糊精提高2.3倍，如图8所示。Under the optimal reaction conditions (γ-cyclodextrin:caffeic acid ratio of 1:64 in the cyclodextrin metal organic framework complex, loading time of 900 minutes, and loading temperature of 40°C), coffee in the prepared complex The loading rate of the acid is 2.3 times higher than that of the same molar amount of γ-cyclodextrin, as shown in Fig. 8 .
本申请还通过实验发现，在最优负载条件下(环糊精金属有机框架复 合物中γ-环糊精：咖啡酸摩尔比为1：64、负载时间为900分钟、负载温度为40℃)，环糊精金属有机框架对咖啡酸的载药率可达16.52％，高于采用同等摩尔量的γ-环糊精对咖啡酸的载药率7.28％。The present application also found through experiments that under optimal loading conditions (γ-cyclodextrin:caffeic acid molar ratio in cyclodextrin metal organic framework complex is 1:64, loading time is 900 minutes, loading temperature is 40°C) , the drug loading rate of cyclodextrin metal organic framework to caffeic acid can reach 16.52%, which is higher than the drug loading rate of caffeic acid with the same molar amount of γ-cyclodextrin, which is 7.28%.
以下以最优反应条件的实施例进行举例说明：Illustrate with the embodiment of optimum reaction condition below:
实施例1Example 1
(1)在烧杯内加入γ-环糊精(648mg，0.5mmol)、氢氧化钾(256mg，4.56mmol)和超纯水(20mL)，室温下搅拌并用0.45μm的水系滤膜过滤得到溶液1；(1) Add γ-cyclodextrin (648mg, 0.5mmol), potassium hydroxide (256mg, 4.56mmol) and ultrapure water (20mL) into a beaker, stir at room temperature and filter with a 0.45μm water filter to obtain solution 1 ;
(2)甲醇(12mL)预先置于超声管后，将溶液1置于超声管，形成乳白色的溶液2，将超声管放入温度为60℃的水浴锅内，静置15min得到澄清透明溶液3；(2) After methanol (12mL) was placed in the ultrasonic tube in advance, solution 1 was placed in the ultrasonic tube to form a milky white solution 2, and the ultrasonic tube was placed in a water bath at a temperature of 60°C, and stood for 15 minutes to obtain a clear and transparent solution 3 ;
(3)溶液3进行超声处理，并于超声处理开始后迅速加入聚乙二醇(8000)(256mg)，反应结束后得到粗产物；(3) Solution 3 was sonicated, and polyethylene glycol (8000) (256 mg) was added quickly after the sonication started, and the crude product was obtained after the reaction;
(4)将粗产物从超声管转移到烧杯，并静置1h，将沉淀物用甲醇离心洗涤3次，离心分离后，再将沉淀物分散于甲醇中；(4) Transfer the crude product from the ultrasonic tube to a beaker, and let stand for 1 h, centrifuge the precipitate with methanol for 3 times, and after centrifugal separation, disperse the precipitate in methanol;
(5)将离心分离后的产物放入真空干燥箱中，在真空条件下50℃干燥12h，冷却至室温后，得到环糊精金属有机框架材料；(5) Put the centrifuged product into a vacuum drying oven, dry at 50°C for 12 hours under vacuum conditions, and cool to room temperature to obtain a cyclodextrin metal organic framework material;
(6)将50mg环糊精金属有机框架材料置于53.25mL浓度为8mg/mL的咖啡酸乙醇溶液中(环糊精金属有机框架材料中γ-环糊精与咖啡酸摩尔比1：64)，采用磁力搅拌方式在40℃保持转速180rpm，并持续孵育15小时，期间保持避光状态；(6) Put 50 mg of cyclodextrin metal organic framework material in 53.25 mL of ethanol solution of caffeic acid with a concentration of 8 mg/mL (the molar ratio of γ-cyclodextrin to caffeic acid in cyclodextrin metal organic framework material is 1:64) , using magnetic stirring method to maintain the rotation speed of 180rpm at 40°C, and continue to incubate for 15 hours, during which time it is kept in a dark state;
(7)将孵育结束后的溶液在5000rpm条件下离心，弃去上清液后采用滤纸吸干残余溶剂，将沉淀至于50℃条件下真空干燥5小时后，得到负载咖啡酸的环糊精金属有机框架复合物。(7) Centrifuge the solution after incubation at 5000rpm, discard the supernatant, blot the residual solvent with filter paper, dry the precipitate under vacuum at 50°C for 5 hours, and obtain caffeic acid-loaded cyclodextrin metal Organic framework complex.
本实施例合成的负载咖啡酸的环糊精金属有机框架复合物的粉末X射线衍射图谱如图4所示，由图4可知，本实施例制备的负载咖啡酸的环糊精金属有机框架复合物架XRD图谱出峰位置与环糊精金属有机框架相吻合，说明了负载咖啡酸不会破坏环糊精金属有机框架结构；相较于咖啡酸以及咖啡酸与环糊精金属有机框架物理共混物的XRD图谱中咖啡酸的特征峰消失，说明咖啡酸处于环糊精金属有机框架的空腔内。The powder X-ray diffraction pattern of the caffeic acid-loaded cyclodextrin metal-organic framework composite synthesized in this example is shown in Figure 4. From Figure 4, it can be seen that the caffeic acid-loaded cyclodextrin metal-organic framework composite prepared in this example The position of the peak in the XRD pattern of the shelf coincides with that of the metal-organic framework of cyclodextrin, indicating that the loading of caffeic acid will not destroy the structure of the metal-organic framework of cyclodextrin; The characteristic peak of caffeic acid in the XRD pattern of the mixture disappeared, indicating that caffeic acid was in the cavity of cyclodextrin metal-organic framework.
本实施例合成的负载咖啡酸的环糊精金属有机框架复合物的红外光谱图如图6所示，本实施例制备的负载咖啡酸的环糊精金属有机框架复合物架红外光谱图出峰位置与环糊精金属有机框架相吻合，说明了负载咖啡酸不会破坏环糊精金属有机框架结构；相较于咖啡酸以及咖啡酸与环糊精金属有机框架物理共混物的红外光谱图中咖啡酸的特征峰变弱甚至部分消失，说明咖啡酸处于环糊精金属有机框架的空腔内。本实施例得到了目标结构的产物。The infrared spectrum of the caffeic acid-loaded cyclodextrin metal-organic framework compound synthesized in this example is shown in Figure 6, and the infrared spectrum of the caffeic acid-loaded cyclodextrin metal-organic framework compound prepared in this example shows a peak The position coincides with the metal-organic framework of cyclodextrin, indicating that the loading of caffeic acid will not destroy the structure of the metal-organic framework of cyclodextrin; compared with the infrared spectrum of caffeic acid and the physical blend of caffeic acid and cyclodextrin metal-organic framework The characteristic peaks of caffeic acid became weaker or even partially disappeared, indicating that caffeic acid was in the cavity of cyclodextrin metal-organic framework. In this example, the product of the target structure was obtained.
本实施例合成的环糊精金属有机骨架的形貌如图5所示，仍具有一定的规整几何外型。The morphology of the cyclodextrin metal-organic framework synthesized in this example is shown in Figure 5, and still has a certain regular geometric shape.
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (14)

  1. 一种基于咖啡酸的复合材料的制备方法，其特征在于，包括：A method for preparing a composite material based on caffeic acid, comprising:
    将由γ-环糊精制备得到的环糊精金属有机框架材料暴露于咖啡酸的短链醇溶液中，孵育处理；孵育处理过程中所述环糊精金属有机框架材料与咖啡酸的短链醇溶液之间动态接触。Expose the cyclodextrin metal-organic framework material prepared by gamma-cyclodextrin to a short-chain alcohol solution of caffeic acid, and incubate; during the incubation process, the cyclodextrin metal-organic framework material and the short-chain alcohol of caffeic acid Dynamic contact between solutions.
  2. 根据权利要求1所述的制备方法，其特征在于，所述环糊精金属有机框架材料与咖啡酸的短链醇溶液的配比以环糊精金属有机框架材料中γ-环糊精与咖啡酸的摩尔比为1：25～70计。The preparation method according to claim 1, characterized in that the ratio of the cyclodextrin metal organic framework material to the short-chain alcohol solution of caffeic acid is based on the ratio of γ-cyclodextrin and coffee in the cyclodextrin metal organic framework material The molar ratio of acid is 1:25-70.
  3. 根据权利要求1所述的制备方法，其特征在于，所述孵育处理的时间为500min～1000min。The preparation method according to claim 1, characterized in that, the time of the incubation treatment is 500min-1000min.
  4. 根据权利要求1或3所述的制备方法，其特征在于，所述孵育处理的温度为30℃～60℃。The preparation method according to claim 1 or 3, characterized in that the temperature of the incubation treatment is 30°C-60°C.
  5. 根据权利要求1所述的制备方法，其特征在于，所述环糊精金属有机框架材料由如下方法制备：The preparation method according to claim 1, wherein the cyclodextrin metal organic framework material is prepared by the following method:
    将同时分散有γ-环糊精和氢氧化钾的水溶液超声混合后置于水浴中进行水浴反应，水浴反应结束后再次超声并在超声同时向所得混合液中加入聚乙二醇，得粗产物；将所得粗产物经洗涤、干燥后即得所述环糊精金属有机框架材料；The aqueous solution dispersed with γ-cyclodextrin and potassium hydroxide is ultrasonically mixed and then placed in a water bath for water bath reaction. After the water bath reaction is completed, ultrasonically again and polyethylene glycol is added to the resulting mixed solution while ultrasonically to obtain a crude product ; The obtained crude product is washed and dried to obtain the cyclodextrin metal organic framework material;
    所述水溶液中γ-环糊精和氢氧化钾的摩尔比为1：5～10；The molar ratio of γ-cyclodextrin and potassium hydroxide in the aqueous solution is 1:5-10;
    所述聚乙二醇的分子量为8000，加入的聚乙二醇与γ-环糊精的摩尔比为0.06～0.07：1；The molecular weight of the polyethylene glycol is 8000, and the molar ratio of the added polyethylene glycol to γ-cyclodextrin is 0.06-0.07:1;
    所述水浴反应的温度为55℃～65℃。The temperature of the water bath reaction is 55°C to 65°C.
  6. 根据权利要求1所述的制备方法，其特征在于，所述短链醇为无水甲醇或无水乙醇。The preparation method according to claim 1, characterized in that, the short-chain alcohol is absolute methanol or absolute ethanol.
  7. 根据权利要求1所述的制备方法，其特征在于，所述动态接触为搅拌或震荡；搅拌或震荡的转速为100rpm～400rpm。The preparation method according to claim 1, characterized in that the dynamic contact is stirring or shaking; the rotation speed of stirring or shaking is 100rpm-400rpm.
  8. 根据权利要求1所述的制备方法，其特征在于，孵育处理完成后还包括后处理，所述后处理包括：将孵育处理完成后的混合液离心，弃去上清液后进行真空干燥。The preparation method according to claim 1, characterized in that after the incubation treatment is completed, post-treatment is also included, and the post-treatment comprises: centrifuging the mixed solution after the incubation treatment, discarding the supernatant and then vacuum-drying.
  9. 根据权利要求8所述的制备方法，其特征在于，所述真空干燥的 条件为：40～60℃条件下真空干燥4～6小时。The preparation method according to claim 8, characterized in that the vacuum drying condition is: vacuum drying at 40-60°C for 4-6 hours.
  10. 根据权利要求1所述的制备方法，其特征在于，所述环糊精金属有机框架材料的最小构筑单元的化学式为[(C 48H 80O 40)(KOH) 2] 6； The preparation method according to claim 1, wherein the chemical formula of the smallest building unit of the cyclodextrin metal organic framework is [(C 48 H 80 O 40 )(KOH) 2 ] 6 ;
    1分子量环糊精金属有机框架材料含有6个γ-环糊精。1 molecular weight cyclodextrin MOF material contains 6 γ-cyclodextrins.
  11. 权利要求1～10任一项权利要求所述制备方法制备得到的基于咖啡酸的复合材料。The caffeic acid-based composite material prepared by the preparation method according to any one of claims 1 to 10.
  12. 根据权利要求11所述的基于咖啡酸的复合材料，其特征在于，所述基于咖啡酸的复合材料包括由γ-环糊精制备的环糊精金属有机框架材料和负载于所述环糊精金属有机框架材料上的咖啡酸；所述咖啡酸处于环糊精金属有机框架的空腔内。The caffeic acid-based composite material according to claim 11, wherein the caffeic acid-based composite material comprises a cyclodextrin metal-organic framework material prepared from γ-cyclodextrin and a cyclodextrin metal-organic framework material loaded on the cyclodextrin Caffeic acid on a metal organic framework material; the caffeic acid is within the cavities of a cyclodextrin metal organic framework.
  13. 根据权利要求12所述的基于咖啡酸的复合材料，其特征在于，所述基于咖啡酸的复合材料中，咖啡酸的负载量为基于咖啡酸的复合材料总质量的15～18％。The caffeic acid-based composite material according to claim 12, characterized in that, in the caffeic acid-based composite material, the loading amount of caffeic acid is 15-18% of the total mass of the caffeic acid-based composite material.
  14. 一种基于咖啡酸衍生物的复合材料，其特征在于，所述基于咖啡酸衍生物的复合材料包括由γ-环糊精制备的环糊精金属有机框架材料和负载于所述环糊精金属有机框架材料上的咖啡酸衍生物；所述咖啡酸衍生物处于环糊精金属有机框架的空腔内。A composite material based on caffeic acid derivatives, characterized in that the composite material based on caffeic acid derivatives comprises a cyclodextrin metal-organic framework material prepared by gamma-cyclodextrin and a metal-organic framework material loaded on the cyclodextrin A caffeic acid derivative on an organic framework material; the caffeic acid derivative is in the cavity of a cyclodextrin metal organic framework.
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